A fresh look at ensembles: Derivative discontinuities in density functional theory
A fresh look at ensembles: Derivative discontinuities in density functional theory
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重新审视系综：密度泛函理论中的导数不连续性
DOI：
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
G. Chan
中科院分区：
文献类型：
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作者：
G. Chan
我们提出了零温度系综自旋密度泛函理论。我们在 Kohn-Sham 形式主义和混合精确交换理论（例如 Hartree-Fock-Kohn-Sham 形式主义）的背景下讨论由导数不连续性产生的系综量，包括不消失的渐近势和带隙位移。我们描述并实现了在原子和分子系统中计算这些量的通用方法。最后，我们讨论我们的结果如何解释现有泛函的缺陷，以及如何构造新泛函，通过检查 H^(+)_2 的解离来说明我们的结论。
We present a zero temperature ensemble spin density functional theory. We discuss the ensemble quantities that arise from derivative discontinuities, including the nonvanishing asymptotic potential and band gap shift, in the context of the Kohn–Sham formalism, and hybrid exact exchange theories, such as the Hartree–Fock–Kohn–Sham formalism. We describe and implement a general method of calculating these quantities in atomic and molecular systems. Finally we discuss how our results explain the deficiencies of existing functionals, and how new functionals should be constructed, illustrating our conclusions by examining the dissociation of H^(+)_2.